Process for dyeing hair and composition therefor

ABSTRACT

A keratin fiber dye composition which comprises a solvent and a dyeing amount of a dye compound having the formula:   IN WHICH R is selected from the group consisting of lower alkyl, hydroxy alkyl, carboxyalkyl, carbethoxyalkyl, carbamylalkyl, haloalkyl, aminoalkyl, aminodialkyl, alkylaminodialkyl, alkyl morpholino, alkyl piperidino, having one-six carbon atoms on each mentioned alkyl portion, Z is selected from the group consisting of   GROUP CONSISTING OF METHYL AND NO2, and R&#39;&#39;&#39;&#39; is selected from the group consisting of hydrogen and lower alkyl having one-six carbon atoms, AND R1 is selected from the group consisting of lower alkyl, lower hydroxyalkyl, lower alkoxyalkyl, and   IN WHICH N IS A WHOLE NUMBER BETWEEN TWO AND SIX INCLUSIVE, AND R2 and R3, which may be identical or different, are selected from the group consisting of hydrogen, lower alkyl, lower hydroxyalkyl, and with the nitrogen atom adjacent R2 and R3 may form morpholino and piperidino, each R1, R2, R3 having one-six carbon atoms on their alkyl portion, AND THE PROCESS OF DYEING KERATIN FIBERS.

United States Patent [72] Inventors Gregoire Kalopissis Paris; Andree Bugaut, Boulogne-sur-Seine; Vaban Zorayan, En ghien-les-Bains, all of France [21] Appl. No. 728,750 [22] Filed May 13, 1968 [45] Patented Nov. 2, 1971 [73] Assignee LOreal Paris, France [32] Priorities May 16, I967 [33] Luxembourg May 16, 1967, Luxembourg, No. 53,677; May 16, 1967, Luxembourg, No. 53,678

[54] PROCESS FOR DYEING HAIR AND COMPOSITION THEREFOR 4 Claims, No Drawings [52] U.S.Cl 8/10, 8/1 I, 8/l0.l, 260/553, 260/470, 260/247.2, 260/471, 260/490, 260/562, 260/556, 260/553, 260/293,

[51] Int. Cl D06p 3/04 [50] Field of Search 8/10, ll; 260/573, 556, 562 RH, 570.5

[ References Cited FOREIGN PATENTS 758,111 5/1967 Canada 8/11 Primary Examiner--George F. Lesmes Assistant Examiner- Patricia C. Ives Attorney-Holcombe, Wetherill & Brisebois ABSTRACT: A keratin fiber dye composition which comprises a solvent and a dyeing amount of a dye compound having the formula:

I1IHRI in which R is selected from the group consisting of lower alkyl, hydroxy alkyl, carboxyalkyl, carbethoxyalkyl. carbamylalkyl, haloalkyl, aminoalkyl, aminodialkyl, alkylaminodialkyl, alkyl morpholino, alkyl piperidino, having one-six carbon atoms on each mentioned alkyl portion, Z is selected from the group consisting of in which R' is selected from the group consisting of methyl and N0 and R" is selected from the group consisting of hydrogen and lower alkyl having one-six carbon atoms,

and R, is selected from the group consisting of lower alkyl. lower hydroxyalkyl, lower alkoxyalkyl, and

having one-six carbon atoms on their alkyl portion, and the process ofdyeing keratin fibers.

PROCESS FOR DYEING HAIR AND COMPOSITION THEREFOR It is an object of the present invention to provide a new chemical compound responding to the formula:

in which R represents a lower alkyl, which may or may not be substituted, and in particular a hydroxyalkyl, carboxyalkyl, carbethoxyalkyl, carbamylalkyl, halogenoalkyl or aminoalkyl radical. The aminoalkyl may, or may not be substituted on the amine function, the nitrogen atom of which may form part of a heterocyclic ring. In the above formula 2 may be an radical, or a radical, with R representing a hydrogen atom, a methyl group, or an NO group, and R" representing a hydrogen atom, or a lower alkyl, while R represents a lower alkyl, a lower hydroxyalkyl, or a chain in which n is a whole number between two and six inclusive, and R and R which may be identical or different, represent a hydrogen atom, a lower alkyl, or a lower hydroxyalkyl, while the nitrogen atom adjacent R and R may form therewith a heterocyclic radical such as a morpholino or piperidino radical and radicals of the alkyl portions of the radicals R, R", R,, R and R having 1-6 carbon atoms.

Another object of the present invention is to provide new quaternary derivatives corresponding to the compounds of formula (I), when these compounds have a quaternizable tertiary amine function.

It should be noted that the compounds of formula (I) are particularly adapted to be used to dye keratinic fibers in general, and especially hair. They have an excellent affinity for keratinic fibers, good stability when exposed to light and inclement weather, and are readily soluble in water.

A further object of the present invention is to provide a composition for dyeing human hair essentially characterized by the fact that it comprises, in solution, at least one dye selected from the group consisting of the compounds responding to formula (I) and their quaternary derivatives.

The dyeing compositions according to the invention are preferably simple aqueous solutions having a pH value lying generally between 4 and 10, and preferably between 7 and 10.

Moreover, the dyeing compositions according to the invention may comprise various ingredients currently used in hair dyeing compositions, such for example as organic solvents, thickening agents, detergents, emollients, perfumes and lacquers. The dyes according to the invention may also be mixed with each other and with other dyes such as nitro dyes, azo dyes, anthraquinone dyes, or any other type of dye conventionally used to dye hair.

The application of these dyeing compositions to the hair does not necessitate the addition of an oxidizing agent. The time of contact with the hair may vary within broad limits, but falls preferably between S and 30 minutes. The temperature at which said compositions are applied may also be varied, but they are preferably used at room temperature. The concentration of the dye may be varied within broad limits, but lies preferably between 0.1 percent and 3 percent by weight.

It is a further object of the present invention to provide a method of dyeing hair essentially characterized by the fact that a dyeing composition as hereinbefore defined is applied to the hair for between 5 and 30 minutes, and the hair is then washed, rinsed, and dried.

The present invention also comprises a method of preparing the compounds of formula (I) essentially characterized by the fact that, in the first step parahalogenometanitranilines or arylsulfonamides responding to the formula:

in which R has the significance hereinbefore indicated, and X represents a halogen atom (preferably chlorine) are alkylized. This step is followed in the case of the arylsulfonamides of forin which X and R have the significances hereinbefore indicated. Then, in a second step, the compound according to formula III is amidified to transform it into a derivative responding to the formulai IYIRZ in which X and R have the significances hereinbefore indicated and Z represents either an radical, in which R has the significances hereinbefore indicated, or a radical in which R has the significance hereinbefore indicated. This is followed by a third step in which the compound of formula IV is reacted with an amine having the formula R NH in which R has the significance hereinbefore indicated.

The compounds responding to formula (I) may be quaternized in a conventional manner, using a quaternizing agent such as methyl sulfate or an alkyl or aryl halide.

It is also an object of the present invention to provide the intermediates obtained in the course of the above-described process, per se. In particular, it is desirable to obtain chemical compounds responding to the formula:

(III) and their salts (particularly their hydrohalides) as well as the chemical compounds responding to the formula:

IIIRZ and their salts (particularly their hydrohalides). In these formulas R, X and Z have the significances hereinbefore indicated.

The present invention also encompasses the methods of making the new intermediates responding to formulas (III) and (IV). These processes consist of the first and second steps of the method of making the compound of formula (I), as hereinbefore described.

In order that the invention may be better understood, several examples of methods of making the intermediates of formulas (Ill) and (IV) and the final compound of formula (I), as well as several dyeing compositions made with the compounds of formula (I) will now be described.

In the first series of examples, the preparation of several compounds responding to formula (III) will be described.

EXAMPLE I Preparation of 2-nitro-4-N-,B-hydroxyethylamino chlorobenzene by direct alkylation A mixture containing 0.070 mo] (12 g.) of 2-nitro-4-amino chlorobenzene is heated in a boiling water bath with 0.14 mol (25 g.) of 70 percent glycol bromohydrin, cc. of water and 7 g. of calcium carbonate. After heating for 2 hours, 0.14 mols of 70 percent glycol bromohydrin and 7 g. of calcium carbonate is added and the heating continued for another 2 hours. After cooling, 150 cc. of normal hydrochloric acid is poured in, and the mixture filtered. After alkalizing with amrnonia, drying yields 13.5 g. of a product which contains a little 2-nitro-4-N-B-hydroxyethylamino chlorobenzene. After recrystallization in a mixture of water and ethanol, 2-nitro-4- N-B-hydroxyethylamino chlorobenzene is obtained. This melts at 72 C. and is the same as the product hereinafter described in Example 4.

EXAMPLE 2 Preparation of 2-nitro-4-N-(fl-diethylaminoethyl)-amino chlorobenzene by direct alkylation This product is prepared by adding diethylaminoethyl hydrobromide to a solution of 2-nitro-4-amino chlorobenzene in the presence of calcium carbonate in water and alcohol which has first been brought to reflux. After keeping this at reflux for 9 hours, it is boiled dry. The filtrate is cooled, and the desired product is isolated in the form of its monohydrobromide. The corresponding base prepared from this monohydrobromide is an oil, which is dissolved hot in a one-tenth normal solution of hydrochloric acid. After cooling, drying yields the monohydrochloride of 2-nitro-4-N-B- diethylaminoethyl-4-amino chlorobenzene which after recrystallization in one-tenth normal hydrochloric acid, melts and decomposes at 191 C., and is the same as the product hereinafter described in Example 5.

EXAMPLE 3 Preparation of N-methyl-parachlorometanitraniline par alkylation with arylsulfonamides First step: alkylation 0.4 mol (125 g.) of 2-nitro-4-benzenesulfonylamino chlorobenzene is dissolved in 600 cc. of a normal sodium hydroxide solution at 30 C. 1.6 mols cc.) of methyl sulfate is added little by little, while keeping the temperature between 35 and 40 C. and the pH value near 9 by successive additions of a normal sodium hydroxide solution. The reaction mixture is then left to stand for 6 hours at room temperature. Cooling, drying and washing then yields 138 g. of crude 2- nitro-4-N-methyl-N-benzene sulfonylamino benzene which, after recrystallization in ethyl acetate, melts at 1 19 C. Analysis of this product shows the following results:

Analysis Calculated for Found c n mclso,

Analysis CAlcululed for Found C,H,N,O,Cl

C 45.08 44.87-44.96 H k 3.72 3.84-3.87 N56 1501 15.15-15.25

EXAMPLE 4 Preparation of N -B-hydroxyethyl-parachlorometanitraniline by alkylation of an arylsulfonamide First step: Alkylation 0.097 mol (30 g.) of 2-nitro-4-N-benzene-sulfonylamino chlorobenzene is dissolved in cc. of a one-half normal sodium hydroxide solution which has first been brought to 60 C. While maintaining the reaction mixture at this temperature, 0.5 mol (33.3 cc.) of glycol chlorohydrin is added drop by drop while stirring vigorously. A five times normal sodium hydroxide solution is added simultaneously to keep the pH between 10.5 and l 1. The mixture is maintained at 60 C. for about 5 hours and then left standing for 12 hours at room temperature. Drying and washing with water yields 34 g. of 2' nitro-4-(N-{3-hydroxyethyl-N-benzenesulfonyl)-amino chlorobenzene which, after recrystallization in methanol, melts at 1 19 C. Analysis of the product yields the following results:

Analysis Calculated for Found C H ,N O,SCl

S 8.97 B.96-9.l4

Preparation of 2-nitro-4-( N-B-diethylaminoethyl )amino chlorobenzene monohydrochloride by alkylation of an aryl sulfonamide First step: alkylation 0.1 mol (31.25 g.) of 2-nitro-4-N-benzenesulfonyl-amino chlorobenzene is dissolved in 100 cc. of a twice normal sodium hydroxide solution which has first been brought to 60 C. While maintaining the reaction mixture at this temperature 016 mol (27.5 g.) of diethylaminoethylchloride hydrochloride in aqueous solution, is added drop by drop, together with 80 cc. of a twice normal sodium hydroxide solution which serves to keep the pH sufficiently alkaline. This reaction mixture is kept at 60 C. for 30 minutes, cooked, acidified with concentrated hydrochloric acid, and, when then dried, yields 36.5 g. of the desired product in the form of its hydrochloride. This crude hydrochloride is purified by crystallization in water, and then converted by addition of a twice normal solution of sodium hydroxide into 2-nitro-4-(N-B- diethylaminoethyl-N-benzenesulfonyl)amino chlorobenzene which, after vacuum drying on P melts at 43C. The analysis of this product yields the following results:

Analysis Calculated for Found c,,n,,n,o,scl

N l0.2l 10.40-40.45

Found Analysis Calculated for CIRHIBNJO'ICIX In a second series of examples the method of preparing several intermediate compound's responding to formula (IV) will now be described.

EXAMPLE 6 Preparation of (N-methyl-N-acetyl) parachlorometanitraniline 0.19 mol of N-methyl-parachlorometanitraniline, prepared as set forth in example 3, is dissolved in 70 cc. of acetic anhydride. This is heated for 15 minutes in a boiling water-bath, and poured into 700 cc. of water. Drying then yields 35 g. of 2- nitro-4-(N-methyl-N-acetyl)amine chlorobenzene, which melts at 114 C.

EXAMPLE 7 Preparation of 2-nitro-4-(N-methyl N-benzenesulfonyl)- amino chlorobenzene 0.19 mol (35.5 g.) of N-methyl-parachlorometanitraniline prepared as set forth in example 3 is dissolved in 175 cc. of pyridine. 0.5 mol (88.25 g.) of benzenesulfochloride is added. After heating to reflux for 5 minutes the mixture is cooled, and drying yields 60 g. of 2-nitro-4-(N-methyl-N-benzcnesulfonyl)-amino chlorobenzene which, after recrystallization in ethyl acetate, melts at 119 C.

EXAMPLE 8 Preparation of 2-nitro-4-(N-benzenesulfonyl-N-[idiethylaminoethyl)-amino chlorobenzene 0.02 mol (6.16 g.) of 2-nitr0-4-N-(B-diethylaminoethyhamino chlorobenzene is dissolved in 30 cc. of pyridine. 0.04 mols, (7.06 g.) of benzenesulfochloride is added. After heating to reflux for 20 minutes, this is poured into cc. of cold water, and subsequent drying yields 8.9 g. of 2-nitro-4-(N- benzenesulfonyl-N-diethylaminoethyl)-amino chlorobenzene monohydrochloride in practically pure form. This hydrochloride, when treated with a twice normal sodium hydroxide solution, yields the corresponding base which, after washing with water and prolonged vacuum drying, melts at 43 C.

EXAMPLE9 Preparation of 2-nitro-4-(N-acetyl-N-B-acetoxyethyl)-amino chlorobenzene 0.04 mol (8.6 g.) of 2-nitro-4-B-hydroxethylamino chlorobenzene is heated for an hour in a boiling water bath while in solution in 15 cc. of acetic anhydride. After driving off the excess of acetic anhydride under vacuum, the residue is dissolved by heating it in a mixture containing 40 percent hexane and 60 percent benzene. After cooling, drying yields 10.5 g. of 2-nitro-4-(N-acetyl-N-B-acetoxyethyl)-amino chlorobenzene which, after recrystallization in the benzene hexane mixture, melts at 60 C. Analysis of this product yields the following results:

Analysis Calculated for Found H H AL In a third series of examples the preparation of certain compounds responding to formula (I) will now be described:

EXAMPLE 10 Preparation of l-N B-diethylaminoethylamino-2-nitro-4-(N'- methyl-N'-benzenesulfonyl) amino benzene Analysis Calculated for Found c,.H .,N.so,c|

The above-described monohydrochloride is treated for 2 hours with at twice normal sodium hydroxide solution, while stirring vigorously. The sodium hydroxide solution is then extracted with methylisobutyl ketone. The methylisobutylketone, which contains the desired product in solution in the form of its base, is washed with water, dried on sodium sulfate, filtered, and the solvent driven off under vacuum to yield the base in the form of a red oil.

EXAMPLE 1 1 Preparation of methyl-fl-[N-(2-nitro-4-N'-methyl-N'- benzenesulfonyl-amino)phenyl]-aminoethyl methyldiethylammonium sulfate Analysis CAlculaled for Found n u l i r EXAMPLE 12 Preparation of l-N-B-hydroxyethylamino-Z-nitro-4-(N'- methyl-N '-benzenesulfonyl)amino benzene Analysis CAlculated for Found is n s p N7: 11.96 12.13-11.92 S X: 9.99 9.17-9.31

EXAMPLE 13 Preparation of l-N-'y-meth0xypropy1amino-2-nitro-4-(N'- methyl-N -benzenesulfonyl)amino benzene 0.1 mol (32.65 g.) of 2-nitro-4-(N'-methyl-N-benzenesulfonyl)amino chlorobenzene which has been prepared as indicated in example 7, is introduced little by little, while stirring, into 2 mols (178 g.) of-y methoxypropylamine which has first been heated to 95 C. The reaction mixture is kept in a boiling water bath for 20-minutes, cooled, and 200 cc. of ice water is then poured in. The product is an orange-colored oil, which crystallizes very easily. Drying yields 37 g. ofpractically pure l-N-y-methoxypropylamino-2-nitro-4-(N'-methyl-N benzenesulfonyl)amino benzene, which, after recrystallization in alcohol, melts at 76 C. Analysis of this product yields the following results:

Analysis Calculated l'or Found CITHHNIIOSS EXAMPLE 14 Preparation of l-y-methoxypropylamino-2-nitro-4-( N- methyl-N-acetyl)-amino benzene 0.1 mol (22.9 g.) of N-methyl-parachlorometanitraniline which has been prepared as described in example 6, is introduced, while stirring, into 1.5 mols (134 g.) of y-methoxypropylamine which has first been heated to 95 C. This reaction mixture is kept at 95 C. for 20 minutes, cooled and poured into 1.250 liters of ice water. This is acidified with hydrochloric acid, dried, and washing with water yields 25 g. of 1-y-methoxypropylamino-2-nitro-4-(N-methyl-N- acetyl)amino benzene which, after recrystallization, melts in toluene at C. Analysis of this product yields the following results:

Analysis Calculated for Found Ia H I J C b 55.52 55.77-55.54 H 6.76 6.85-6.83 N% 14.95 15.11-15.01

EXAMPLE 15 Preparation of 1-N-B-diethylaminoethylamino-2-nitro-4-(N'- B-diethylaminoethyl-N'-benzenesulfonyl)amino benzene 0.05 mol (20.5 g.) of 2-nitro-4-diethylaminoethyl-N- benzenesulfonyl)-amino chlorobenzene, prepared as described in example 8, is introduced into 0.5 mol (58 g.) of diethylethylene-diamine which has first been heated to C. The reaction mixture is kept at this temperature for 30 minutes. The excess of aliphatic amine is driven under vacuum and the oily residue is poured into 200 cc. ofwater. This yields the desired product in the form of a thick oil. The water is decanted; the oil is dissolved in normal hydrochloric acid; the hydrochloric acid solution is filtered and alkalized with a five times normal sodium hydroxide solution. The desired product is then extracted, using methylisobutylketone and the solvent driven off under vacuum, yielding 22.6 g. of practically pure l-N-B-diethylaminoethylamino-2 nitro-4-(N'-B- diethylaminoethyl-N'-benzenesulfonyl)-amino benzene in the form ofa very thick oil. Analysis of this product yields the following result:

Preparation of l-N-y-hydroxypropylamino-2-n1tro-4-(N- methyl-N-acetyl)-amino benzene 0.1 mol (22.9 g.) of 2-nitro-4-(N-methyl-N-acetyl)-amino Found Analysis Calculated for CIIHHNSO4 EXAMPLE 17 Preparation of l-N-,B-diethylaminoethylamino-2-nitro-4-(N B-hydroxyethyl-N-benzenesulfonyl)-amino benzene 0.070 mo] (25 g.) of 2-nitro-4-(NB-hydroxyethyl-N- benzenesulfonyl)-amino chlorobenzene, which has prepared as described in the foregoing example, is introduced into 0.70 mol (81.5 g.) of N, N-diethylethylenediamine which has first been heated to 95 C. The reaction mixture is heated for half an hour in a boiling water bath, and the excess aliphatic amines is then driven off under vacuum. The oily residue obtained in this manner is dissolved in 70 cc. of propanol. After having bubbled dry hydrochloric acid through this iced propanolic solution, drying yields 31 g. of l-N-B- diethylaminoethylamino-2-nitro-4-( N '-B-hydroxyethyl-N benzenesulfonyl) amino benzene monohydrochloride which, after recrystallization in propanol containing 2 percent water, melts and decomposes at 178 C. Analysis of this product yields the following results:

Analysis Calculated for Found n ae a s u 'if TiIss 11.71-11.82-

Several examples will now be given showing how the compounds of formula l are used in hair dyeing compositions.

EXAMPLE 18 The following composition is prepared:

l-N-fi -diethylaminoethylamino-Z-nitro- 4N'-hydroxyethylamino benzene This composition is applied to bleached hair and left thereon for minutes. The hair is then rinsed and shampooed.

A copper mahogany color results.

EXAMPLE 19 The following composition is prepared:

mcthyl-N-acetyl)-amino benzene 1.3 g. Isooctylphenylpolyethoxyethanol 1.5 g. NILOH, q.s.p. pH 9 Water, q.s.p. 100 g.

This composition is applied to 100 percent white hair for minutes. The hair is then rinsed and shampooed and a deep blonde shade results.

EXAMPLE 20 The following dyeing composition is prepared:

l-diethylaminoethylamino-2-nitro-4- N,N-dihydroxethylamino benzene dihydrochloride 0.30 g. Methyl-p-[N(2-nitro-4N'-methyl-N'- benzenesulfonyl-amino)-pneyll-aminoethyl-methyldiethylammonium sulfate 0.l4 g. Isuoclyl phenyl polyethoxy ethanol 1.2 g.

Monoethanolamine, q.s.p. pH 7.5 Water, q.s.. g.

This composition is applied to bleached hair and left thereon for 10 minutes. The hair is then rinsed and shampooed.

A deep mahogany results.

EXAMPLE 21 The following dyeing composition is prepared:

l N'fidiethylaminoethyl amino-2-nitro-4- N-hydr0xyethylamino benzene 0.25 g. lsooctyl phenyl polyethoxyethunol 1.2 g. Lactic acid q.s.p. pH 4 Water q.s.p. I00 g.

This composition is applied to bleached hair and left thereon for 10 minutes. The hair is then rinsed and shampooed.

A purple-violet color results.

The dyes of the invention can be also applied to normal colored hair and without using an oxidizing agent.

The following compounds illustrate the compounds of the invention containing respectively the R, Z, R, R, R,, R and R radicals as before mentioned: l-N-B -hydroxyethylamino-2- nitro-4-(N'-methyl-N'-benzenesulfonyl)amino benzene; l-N- B-diethylaminoethylamino-2-nitro-4-(N'-/3-hydroxyethyl-N- benzene-sulfonyl)-amino benzene; 2-nitro-4-(N-acetyl-N-fiacetoxyethyl)-amino chlorobenzene; methylamino-l,nitro- 2,(N,N-methyl carboxymethyl)amino-4,benzene; N- methylaminol ,nitro-2,(N '-benzenesulfonyl,N'-/3- bromoethl)-amino-4,benzene; 2-nitro-4-N-(B- diethylaminoethyl)-amino chlorobenzene; l-N-B-diethylaminoethylamino-2-nitro-4(N-B-diethylaminoethylamino- N'-benzene-sulfonyl)amino benzene; l-N-y-methoxypropylamino-2-nitro-4-(N'-methyl-N'-benzenesulfonyl)amino benzene; 1-N-'y-diethyl-aminoethylamino-Z-nitro- 4-(N-methyl-N'-benzenesulfonyl) amino benzene.

The following organic solvents may be used as solvent in the dye composition of this invention: benzylic alcohol, phenethyl alcohol, 2-butoxyethanol, cyclo-hexanol and the like.

The ingredients which may be added to the dye composition of this in ention of the conventional type and particularly of the dyes selected from the group consisting of nitro dyes such as 1-hydroxy-2-amino-5-nitro benzene, azo dyes such as Supracide" (Compagnie Francaise des Matieres Colorantes),

Supt-amine (Socit Bayer),

Cibacete" (Socit Ciba) s l te (Imperial Chemical Industries Ltd.

and anthraquinone dyes such as:

Solway" (Imperial Chemical Industries Ltd.),

Cellit (B.A.S.F.) et

Fenacet (General Dye Corp. N.Y.), and the like.

The following compounds illustrate the intermediate compounds of the invention:

1-chloro-2-nitro-4-(N-methyl-N-acetyl)-amino benzene; l-chloro-2-nitro-4-( N-methyl-N-benzenesulfonyl )-amino benzene; 1chloro-2-nitro-4-(N-diethylaminoethyl-N'-benzenesulfonyl) amino benzene; lchloro-2nitro-4-(N-carbomethoxy-ethyl-N-acetyl) amino benzene; 1chloro-2-nitro-4-(N-carbethoxy-ethyl-N-benzenesulfonyl)amino benzene;

l chloro-2-nitro-4-(N-bromoethyl-N-benzenesulfonyl)amino benzene,

and they have the respective formulas /GH /CH; N-COCH; 1y-so,-@

NO; N; 4: C1

0,1315 CHg-CH;0OCCH3 CHg-CHg-N\ III-CO C H; CQHS III-SO;

I NO; C1 61 CHr-CHgBl S03- NCH1'CHr-C OgCgHfi What is claimed is: l. A composition for dyeing keratinic fibers comprising an aqueous solution of a dye havingthe formula wherein R is selected from the group consisting of lower alkyl, hydroxyalkyl, haloalkyl, aminoalkyl, aminodialkyl, and alkylamino-dialkyl, and wherein the alkyl moiety of each has one to six carbon atoms, Z is selected from the group consisting of wherein R is selected from the group consisting of hydrogen methyl and N0 and R" is selected from the group consisting of hydrogen and lower alkyl having one to six carbon atoms, and R is selected from the group consisting of lower alkyl, lower hydroxyalkyl, wherein the alkyl moiety of each has one to six carbon atoms and LII wherein n is an integer of 2-6 inclusive, and R and R each independently are selected from the group consisting of hydrogen, lower alkyl, lower hydroxyalkyl, and the alkyl moiety of each having one to six carbon atoms, said dye being present in amounts of about 0.1-3 weight percent of said composition.

2. The composition of claim 1 having a pH ranging between 4-10 inclusive.

3. The composition of claim 1 wherein the pH ranges between 7-10 inclusive.

4. A process for dyeing hair comprising applying to said hair in amounts effective to dye said hair a composition having a pH of 4-10 and comprising an aqueous solution of a dye having the formula wherein R is selected from the group consisting of lower alkyl, hydroxyalkyl, haloalkyl, aminoalkyl, aminodialkyl, and alkylaminodialkyl, wherein the alkyl moiety of each has one to six carbon atoms, Z is selected from the group consisting of wherein R is selected from the group consisting of hydrogen, methyl and N0 and R" is selected from the group consisting of hydrogen and lower alkyl having one to six carbon atoms and R, is selected from the group consisting of lower alkyl, lower hydroxyalkyl wherein the alkyl moiety of each has one to six carbon atoms and wherein n is an integer of 2-6 inclusive, and R and R each independently are selected from the group consisting of hydrogen, lower alkyl, lower hydroxyalkyl, wherein and the alkyl moiety of each has 1-6 carbon atoms, said dye being present in amounts of about 0.1-3 weight percent of said composition, permitting said composition to remain in contact with said hair for a period of about 5-30 minutes and thereafter washing, rinsing and drying said hair.

1i i t 

2. The composition of claim 1 having a pH ranging between 4-10 inclusive.
 3. The composition of claim 1 wherein the pH ranges between 7-10 inclusive.
 4. A process for dyeing hair comprising applying to said hair in amounts effective to dye said hair a composition having a pH of 4-10 and comprising an aqueous solution of a dye having the formula 